Insecticide and fungicide



' oils have comprised Y that the product shall tionable. Many Patented Aug. 13, 1 r

s PATENT OFFICE msuc'rrcma sun momma William E. Bradley,

to Union Oil Company of Califo geles, CaliL, a corporation of California Los Ane'eles, Calif, rnla,

No Drawing. Application June 8. 1942, Serial 100.448.273

(or. raw-as) '1 Claims.

This invention relates to the production of improved fungicides and insecticides containing synthetic light oils.

In the past it has been common practice to employ naturally occurring petroleum fractions, es-

pecially those fractions boiling in the range of 350 F. to 800 F. in the preparation of insecticides and fungicides. These oils have been used alone or commingled with auxiliary additives designed to produce specific toxic, spreading or emulsifying qualities. For example, typical fly sprays have comprised highly refined kerosene fractions, specific toxic ingredients such as pyrethrum extract, and perfumes. Typical spray oils or fungicide simply highly refined petroleum fractions boilingin the light lubricating oil range. Soluble oil sprays commonly comprised petroleum fractions, soaps, alcohols and water. In all such preparations it is obviousl desirable hav a controlling effect on the insect pest or undesirable fungus and yet be as harmless as possible to human beings, domestic animals, plants and to equipment used in the application. For indoor operation, such as fiy spray, it is further desirable that the oil base have an odor which is very bland or rather pleasing. It is known that many of the insecticidal and fungicidal oils now in use are somewhat toxic to human beings, domestic animals and plants. Furthermore they have a serious destructive action on equipment due to their tendency to dis; solve or swell rubber parts used in the equipment: Finally the odors of some sulfurand nitrogen-containing bodies frequently associated with petroleum fractions. and even the odors of some of the hydrocarbons themselves, are objecpetroleum fractions which have been used in fun icides or insecticides have been heavily treated with strong sulfuric acid or liquid isulfur dioxide for example, in order to remedy to some extent the above undesirable properties.

It is the object of this invention to provide insecticides and fungicides compounded from synthetic oils having insecticidal and fungicidal properties equivalent to those of the petroleum products now in use. but having other properties in marked contrast to those of the petroleum products, namely, (1) a less pronounced and more pleasing odor, (2) relatively low swelling action on natural or synthetic rubbers, (3) relatively low tomcity to human beings, animals, and plants, (4) relative freedom from sulfurand nitrogencontaining impurities, and (5) sufilcient purity and stability as to require only moderate finishing butenes and pentenes,

- suitable 1 finishing treatments may tic.

According to this invention, isoparailinic products boiling substantially pure in the range 350 F. to 800 F. are prepared by any process involving principally almlation of p with monoolefins. The product is then subjected to fractionation and finishing treatment. in either order, and compounded with the desired additives, such as toxic, spreading. or emulsifying agents, antioxidants, etc. The fractionation is preferably carried out continuously, in a vacuum, or using steam. Generally the insecticide base oils such as tly spray base, are fractionally distilled so as to boil within the range ofabout 350 F. to 550 F., while the spray oils such as those used in fungicides, are fractionated so as to boil in the range of about 450 F. to 800 F. The finishing treatment may involve treatment with concentrated or fuming sulfuric acid in the proportions of about one pound H2504 per gallon, or in smaller proportions, followed by water washing, caustic washing and/or distillation. Other conventional also be used, such as clay treatment, with or without a. preceding sulfuric acid treatment: orvapor phase treatment with fullers earth, clay. partly hydrated zinc chloride, etc.

As a specific example of my invention, an isoparafiinie fly spray base was prepared, using as a starting material a sample of heavy alkylate obtained as a bottoms fraction from distillation of the alkylated product from a commercial alkylation plant. "ihe latter was-a conventional plant for continuously reacting isobutane. with employing H1804 as a cata lyst, and was similar to that described in the Re finer, vol. 20, 1941,, page 3'39. ture in this instance comprised about 45 volumes of isobutane and about volumes of approximately 92% sulfuric acid to each volume of ole fins. The debutanized alkylated product from this plant was distilled to obtain a light alkylate for use in aviation gasoline and a heavy alkylate bottoms fraction which, in this case, had a boiling range of approxlmateh 350 to 600 F. and consisted of substantiall pure isoparamns. A portion of this material was steam distiliedto obtain a fraction having a boiling range of approximately 380 to 480 F. This fraction was agitated one minute with 98% E180; in the ratio of 10 pounds acid per barrel of oil and settled for one hour. The oil was then decanted from the acid sludge, washed successively with an equal volume of water and 10% by volume of 2% caustic treatment with acid. clay. suliur dioxide or caus- The reaction mix-' and steam distilled, taking about 95% overhead. This overhead fraction, which tested over 95% isoparafiins, was washed with 5% by volume of 2% caustic soda solution, and compared with a typical high quality kerosene type fiy spray base made in the following manner:

A kerosene fraction of 380 to 480 F. boiling range distilled from crude oil was subjected to extraction with an equal volume of liquid sulfur dioxide at a temperature of about 15 F. .The raflinate" fraction, which contained smaller proportions of aromatic type hydrocarbons, sulfurand nitrogen-containing materials than either the extract fraction or the feed stock, was freed of sulfur dioxide and treated with pounds of 98% H2804 per barrel followed by washing with an equal volume of water and 10% of 2% caustic soda solution successively, as described above.

soda solution,

The characteristics of the two products follow:

Acid treated Lgynthetic eroserg paroiiinic raflina traction Spec. gravity at (50/60 F.'. .787--..;.- .806. gulf?! (GI-Eight per cent by wt- 0.00:. 0.15.

nger n, F;

102' r 404 388. 50 420 417. 00. a 452 454. Approx. viscosity, 8. U. a't'-l00 F., sec. 80 30. Pour int, F Below -90-. About 45. EquaP ol. aniline point, F.. 198 160. Insecticidal value Good Good. Lack of phytocidal sheets"... Excellent Do. Swelling action on rubber, per cent... 1 0 50% to 100%. Odor Excellent Good.

Finished insecticide sprays were prepared from the above two materials by adding to each 0.2% of pyrethrins as a lethal ingredient and a small amount oi perfume. The two products were equally effective insecticides.

The yield of heavy alkylate in the process described above may be improved by (1-) operating at relatively low ratios of isobutane to olefin in (2) alkylating' the feed stock and recycle stream, at relatively high temperatures, particularly above 50 F., and (3) using H2804 of rather low strength, in the neighborhood of 90% or below.

An isoparaifinic spray oil was prepared as follows: Five volumes scribed above, and five were introduced into a vessel equipped with an agitating device. While agitating this mixture at a temperature of about 60 F. One volume of crude di-isobutylene was added in small proportions over a period of one-half hour. After an additional thre hours of agitation the mixture was allowed to settle and the hydrocarbon phase was decanted from the acid phases The hydrocarbon phase was washed with 101% by volume of 2% caustic soda solution and steam distilled to remove that fraction boiling below 480 F. The high boiling residue was treated with 10 pounds of 98% H2304 per barrel followed by water and caustic, as described above, and steam distilled to obtaina distillate having a final boiling point of about 620 F. -,'I'his product was compared with a typical high qualit spray oil made from a petroleum fraction as follows:

A'fraction from crude oil distillation having a boiling range of about 480 to 620 F. was treated with 125% by volume of liquid sulfur dioxide in four counter-current stages at a temperature of about 50 F. The raiflnat fraction after removal of; all sulfur dioxide was agitated one-half hour with sulfuric acid in the ratio of 50 pounds of 103% H2804 perbarrel of all.

volumes of 98% H2504 7 After two hPurs' Of particular interest are parative tests of the two spray oils follow:

Synthetic Typical lsopara c spray oil Specific gravity at 60 F./60 F .835

Engleidist'n, F.:

90 o Sulfur, per cent by wt S. U. viscosity at 100 F., se Pour int, "F Equa vol. an. pt., Swelling action on rubber, per cent. Unsulfonated residue, de Ong, per cent. 57 Lack of phiwtocidal efiects-- Insecticide value Fungicidal value th above values for percent unsulfonated residue which is generally considered to be a measure of the quality of the spray oil as being non-injurious to plants. The two sprayoils described above were emulsified with water after addition of 0.5% of tetraethylene glycol monolaurate and it was found that the product containing the isoparafllnic material, in spite of its low de Ong value was relatively noniniurious to plants and foliage. Low specific gravity, low sulfur content, low pour point and high aniline point also distinguish the synthetic isoparafiinic oils of both this table and the earlier table from the typical. petroleum products.

The relative toxicity to animals of the above described synthetic isoparafilnic oils, compared to of heavy alkylate," as dethe petroleum fractions may be deduced from data included in Report No. of the Medical Research Council of the British Industrial Health Research Board, published as a book entitled "Toxicity of Industrial Organic Solvents" by His Majesty's StationeryOfiice, London in 1937. In the course of a discussion of the relative toxicities of various types of hydrocarbon mixtures it is stated that for mixtures containing principally cycloparafiins and acyclic paraflins, the toxicity increases with increasing cycloparaifin concentration, and alsowith increasing specific gravity. On this basis the isoparafilnic oils described above in which naturally occurring antioxidants have been removed in the refining process.

the ranle of about 350 1''. to

While the character-of certain materials has been described in detail in order to clarify the significance of the invention, it is not intended to impose limitations thereby. For example the alkylation process may involve other catalysts, such as I-IF' or AlCla, etc., other those produced from cracking, chlorination and dehydrochlorination, oxidation and dehydration, eta, other isoparaiiinic ieed stocks, and other apparatus or operating conditions. Theemulsitying a ents used with the isoic spray oils to: emulsions, suspensions, or soluble oils may include not only tetraethylene glycol monolaul'ate' but other esters, soaps, alcohols, etc.. suchas calcium caseinate, saponin. soaps of whale oil, their oil. cottonseed oil, oocoanut oil. etc.. and their fatty acids. fatty acids themselves, phenol homoiogs, Bordeaux mixture, and resin. Some or these mayalso have other effects such as spreading, stlckinz. or toxic silicate. Other auxiliary toxic agents may include nicotine suli'ate. rotenone. etc, It will lie/apparent to those skilled in the art that numerous other modifications may be made without departing trom the scope of the iollowing claims- I claim:

1. A process for the treatment of areas infested .with tunsus and insects. which comprises spraying said areas with a material comprising a substantially pure isoparamnic oil boiling in about 800 1'',

2. A process for the treatment of areas infestoleilns such as A pure lsoparamnic oil volvins alkylation 0! ed with insects, which comprises spraying said areas with a material pure isopc oil boiling 350 F. to about 550 F.

3. A process for the treatment of areas infested with fungus, which comprises spraying said areas with a material comprising a substantially boilingin the range of about 450 F. to about 800 F.

et- An insecticide consisting essentially of small amounts of pyrethrins, dissolved in a substantially pure isoparc base oil boiling within the range350-F. to 550 F.

5. An insecticidal and fungicidal spray emulsion consisting essentially of a substantially pure mop'arc base oil boiling in the range 350 F. to 800 E, an emulsifying agent. and water.

6. An 'insecticideconsisting essentially of small amounts of pyrethrins and a perfume, dissolved in a substantially pure isoparafnnic oil boiling in the range of approximately 350 F. to 550 F. and prepared by a process involving alkylation of an olefin and an isoparamn'.

7. An insecticidal and fungicidal spray sion consisting essentially of an emulsifying agent. water, and a substantially pure isoparaiflnic oil boiling in the range 01' approximately 450 F. to 800 F. and prepared by a. process inan olefin and an isoparaflin, said oil having a specific gravity of about 0.835 and a do On: unsullonated residue of about 57%.

, p E. BRADLEY in the range of about comprising a substantially emul- 

